Small Gold(I) and Gold(I)–Silver(I) Clusters by C−Si Auration

Auration of o‐trimethylsilyl arylphosphines leads to the formation of gold and gold–silver clusters with ortho‐metalated phosphines displaying 3c–2e Au−C−M bonds (M=Au/Ag). Hexagold clusters [Au(6)L(4)](X)(2) are obtained by reaction of (L−TMS)AuCl with AgX, whereas reaction with AgX and Ag(2)O leads to gold–silver clusters [Au(4)Ag(2)L(4)](X)(2). Oxo‐trigold(I) species [Au(3)O](+) were identified as the intermediates in the formation of the silver‐doped clusters. Other [Au(5)], [Au(4)Ag], and [Au(12)Ag(4)] clusters were also obtained. Clusters containing PAu−Au−AuP structural motif display good catalytic activity in the activation of alkynes under homogeneous conditions.